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mater.scichina.com link.springer.com Published online 19 May 2020 | https://doi.org/10.1007/s40843-020-1305-6

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SPECIAL ISSUE: Advanced Photocatalytic Materials

Oxygen vacancies in metal oxides: recent progress

towards advanced catalyst design
1,2 1,2 1,2* 1,2* 3*
Guoxin Zhuang , Yawen Chen , Zanyong Zhuang , Yan Yu and Jiaguo Yu

ABSTRACT Energy crisis and environmental problems ur-
gently drive the proposal of new strategies to improve human
wellbeing and assist sustainable development. To this end,
scientists have explored many metal oxides-based photo-
catalysts with high stability, low cost, earth abundance, and
potentially high catalytic activity relevant for key applications
such as H2O splitting, CO2 reduction, N2 fixation, and ad-
vanced oxidation of pollutants. In these metal oxides, oxygen
vacancies (OVs) are ubiquitous and intrinsic defects with
pronounced impacts on the physicochemical properties of the
catalysts, which may open new opportunities for obtaining
efficient metal oxides. The thorough understanding of the
structural and electronic nature of OVs is necessary to de-
termine how they serve as catalytically active sites. In this
review, we summarize the origin of OVs, the strategies to in-
troduce OVs, as well as the fundamental structure-activity
relationships to relate these crystal defects to catalyst prop-
erties including light absorption, charge separation, etc. We
emphasize the mechanism of OVs formation and their effects
on the intrinsic catalytic characteristics of the metal oxides.
We also present some multicomponent catalytic platforms
where OVs contribute to catalysis via synergy. Finally, op-
portunities and challenges on engineering defects in photo-
catalysts are summarized to highlight the future directions of
this research field.
Keywords: oxygen vacancy, catalysis, defect engineering, energy
and environment, metal oxide
INTRODUCTION
As a result of population growth and the process of in-
dustrialization, fossil fuels including coal, oil, and natural
gas are being rapidly consumed, which gives rise to en-
vironmental issues like the emission of greenhouse gases
and the discharge of hazardous waste. Technologies for
safe and clean energy are desired to cut back the rising
consumption of fossil fuels. Consequently, sunlight-dri-
ven catalytic reactions relevant for a myriad of applica-
tions such as H2O splitting, CO2 reduction, N2 fixation,
and advanced oxidation of pollutants, all meaningful for
improving the wellbeing of mankind and ensuring the
sustainable development of the society, have gained in-
creasing attention. To this end, many metal oxides-based
photocatalysts (e.g., TiO2 [1–7], ZnO [8,9], MoO3 [10,11],
CuO [12–15], MnO2 [16,17], VO2 [18], WO3 [19], and
CoOx [20]) have been explored, owing to their high sta-
bility, low cost, abundance in the Earth, and appealing
catalytic activity. It is well acknowledged that both high
catalytic efficiency and high selectivity are indispensible
for photocatalytic reactions to industrial application.
Despite decades of research exploring advanced photo-
catalysts, as of today the development of economic and
efficient catalysts remains challenging in both funda-
mental research and practical applications. The efficiency
of photocatalyst reported is often limited by the in-
adequate absorption of visible light, excessive charge re-
combination, as well as the poor reactivity of the so-called
inert molecules (e.g., CO2, N2) in cataltyic reactions.
Point defects such as oxygen vacancies (OVs) are ubi-
quitous in metal oxides, have a pronounced effect on the
physical and chemical properties of the material, and thus
open new opportunities for obtaining efficient metal
oxide catalysts [21–23]. The concept of OV was proposed
in the 1960s by Tompkins et al. [24], in which OV was
supposed to be a kind of species in solid superficial
chemistry. Subsequently, OV was found to exist in many

1
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, China
2
Key Laboratory of Advanced Materials Technologies (Fuzhou University), Fujian Province University, Fuzhou 350108, China
3
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, China
*
Corresponding authors (emails: zyzhuang@fzu.edu.cn (Zhuang Z); yuyan@fzu.edu.cn (Yu Y); jiaguoyu@yahoo.com (Yu J))

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 1
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oxides and account for their distinct physicochemical
properties (e.g., optical properties [25,26] and electrical
conduction [27,28]) with reference to stoichiometric
oxides. Some studies focused on the production of OVs
[29] and the diffusion of OVs in oxides [30,31]. Extensive
studies on OVs started from 2000 when researchers found
that OVs could act as active sites in catalytic reactions to
adsorb substrates [32,33]. In the study on black TiO2,
researchers further found that OVs played critical roles in
boosting the solar absorption of oxides [34]. Since then
enormous efforts have been devoted to the regulation of
OVs for advanced photocatalysis [35–37], electrocatalysis,
[38,39] and thermal catalysis [40,41].
To date, the nature and content of OVs in metal oxides
have been shown to directly affect catalyst functions in
reactions including H2 evolution [42–44], NO reduction
[12], CO oxidation [45,46], C6H5Cl destruction [47], etc.
Prior studies have revealed that OVs improve the catalytic
performance mainly by modulating light absorption [48],
charge transfer [49–52], molecular fixation [21], and/or
catalyst conductivity [53,54]. Several aspects should be
considered when evaluating the impact of OVs on the
photocatalyst. For example, sometimes OVs serve as
charge separation centers to improve carrier separation
efficiency. Huo et al. [55] found that OVs-rich Bi2WO6
allowed stronger photocatalytic NO oxidation compared
with its stoichiometric counterpart. From density func-
tional theory (DFT) calculations, they found that a new
defect level associated with OVs was generated near the
Fermi level, which increased the photoabsorption and
electronic conductivity, suppressed the recombination of
electron–hole, and prolonged the lifetime of carriers. OVs
may also create unsaturated coordination sites (e.g., edge,
corner, or terrace), which are more suitable for reactions
such as H2 evolution and CO2 reduction to take place. As
of now, the intrinsic functions of OVs on catalytic reac-
tion remain elusive and controversial, which hinders the
strategic rational design of catalyst defect. What is worse,
the introduction of OVs to metal oxides is hard to con-
trol. OVs in catalysts have been generated by (i) thermal
Table 1 Reaction energy (in eV) of OV creation on the In2O3 (110) surface in different sites (D1, D2, D3, D4, D5 and D6) by thermal desorption and
by reduction. Adapted with permission from Ref. [59], Copyright 2013, American Chemical Society.
Reaction equation
a
p-In2O3(110) → OV-In2O3−x(110) + ½ O2
b
p-In2O3(110) + H2 → OV-In2O3−x(110) + H2O
c
p-In2O3(110) + CO → OV-In2O3−x(110) + CO2
a) Thermal decomposition; b) H2 reduction; c) CO reduction.
2 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
treatment under vacuum or in an inert atmosphere (He,
N2, and Ar), (ii) chemical reduction, (iii) ion doping, and
(iv) interfacial engineering, and many of these processes
require tedious procedures with demanding precision
under particular time, temperature, and pressure. A
thorough understanding of the controllable regulation of
OVs and the mechanisms of defect-modulated photo-
catalysis is imperative for effective catalyst design [56–
58]. A comprehensive review of the state-of-the-art in the
regard will help promote further developments in this
important, fascinating, and burgeoning research area.
In this review, we summarize the primary origin and
controllable regulation of OVs in various metal oxides, to
assist the rational design of high-performance OV-
mediated catalysts. We list the viable strategies to control
the OVs in photocatalysts and present the principle of
OVs formation. We put special emphasis on tuning the
electronic structures of oxygen-deficient metal oxide
photocatalysts to manipulate their performance in light
absorption, charge carrier transfer and separation, mo-
lecule capture and activation, and all effects on the
eventual thermodynamics of the catalytic reactions. We
reveal the structure-function relationship of OVs in OVs-
mediated catalytic applications such as pollutant de-
gradation, air purification, H2 production, and CO2 re-
duction. Finally, challenges and prospects are presented.
ORIGIN OF OVs
Lattice O atoms from oxides can either directly enter the
gas phase in the form of O2 (i.e., overflow) or be che-
mically reduced to form OVs in the solid phase. Ye et al.
[59] systematically investigated different conditions that
led to the formation of OVs at different sites on the In2O3
(110) surface (Table 1). The lattice O atoms can either
directly desorb to form O2 or react with H2 or CO to form
H2O or CO2.
MO2 → MO2−x + ½x O2 (g).
The OVs change the perfect periodic arrangement of
the crystal (Fig. 1) as well as the electronic structure
around the OVs [60]. Hence, the electronic charge asso-
ΔE
D1 D2 D3 D4 D5 D6
1.96 1.98 2.35 2.47 2.40 2.14
−0.57 −0.56 −0.19 −0.07 −0.13 −0.40
−1.30 −1.28 −0.91 −0.79 −0.86 −1.12
SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS
0 1 » High-energy particle bombardment (HEPB)
; Oxygen vacancy
Cu doping
Jahn-Teller distortion
Figure 1 Polyhedral representation of a pristine TiO6 octahedron and a
defective octahedron with OV resulting from Cu doping at a Ti site.
Adapted with permission from Ref. [60], Copyright 2019, WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim.
−
ciated with the departed O atom (i.e., 2e ) will redis-
tribute to the surrounding lattice. Because metal oxides
have multiple oxidation states, the resulting extra electron
density localizes primarily on the neighboring cations,
reducing them to a lower valence state [61]. Theoretical
calculations demonstrate that abundant localized elec-
trons will form at the OVs, which affect the physical and
chemical property of metal oxides (e.g., optical char-
acteristics, electron transport, surface structure, etc.) and
provide active sites for catalysis. In addition, OVs on the
surface can strongly attract reactive molecules and thus
change their state. These effects altogether improve the
catalytic performance of the metal oxides that possess
OVs. To facilitate the design and modification of cata-
lysts, it is essential to understand in-depth how OVs are
generated, determine various strategies to regulate OVs,
and rationalize the effects of OVs on both the catalyst
itself and the reaction. The following chapter summarizes
different strategies suitable for generating and manip-
ulating OVs.
STRATEGIES TO CREATE OVs
Numerous synthetic strategies have been developed to
create OVs in metal oxides, e.g., high-energy particle
bombardment, high-temperature calcination, chemical
reduction, ion doping, and tuning the heterostructure
interface, all of which facilitate the escape of O atoms.
Many syntheses require harsh conditions (e.g., high
temperature, anaerobic conditions, etc.) yet allow limited
control of the resulting OVs and cannot be readily gen-
eralized. Uncovering how OVs are generated behind the
common operational parameters is indispensable, because
photocatalytic materials with clearly defined OVs must be
obtained before researchers can evaluate the relationship
between defects and photocatalytic performance and then
establish the related reaction mechanisms.
© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Many studies over past decades have reported that HEPB
offers a promising way to create OVs in metal oxides, and
a possible mechanism of OVs formation via HEPB is also
proposed [21,62–72]. High-energy particles suitable for
HEPB could be electrons, protons, or ions that can pre-
ferentially seize and desorb lattice oxygen on the surface
of oxides. In this way, HEPB induces an overflow of
oxygen from the lattice and generates OVs [21]. To date,
HEPB has successfully produced a myriad of oxygen-
deficient metal oxides, including Co3O4 [21,62], ZnO
[63,73,74], SnCo0.9Fe0.1(OH)6 [64], CeO2 [65,75], TiO2 [76
−78], SnO2 [67,79], SrTiO3 [68], SiO2 [69] and Fe2O3
[70,80]. Knotek and Feibelman [81] found that the elec-
trons with energy higher than 34 eV can desorb surface
oxygen through an interatomic Auger recombination
process. von Soosten et al. [82] suggested that the high-
energy particles with energy over tens of eV would induce
loosely bound O atom to overflow from the surface. In
the case of ZnO, Park et al. [63] further revealed that
high-energy proton tended to interact with oxygen anions
than metal cations, and in that case, HEPB normally
created OVs rather than cation vacancies in ZnO
(Fig. 2a). Furthermore, the oxygen atoms weakly bound
to the cations that have fewer charges or larger ion radius
2+ 3+
(e.g., Zn , In ) are more likely to be released from the
lattice [83]. The advantage of HEPB in creating defects is
that the bombardment with particles of appropriate en-
ergy intensity produces OVs without incurring unwanted
damages to the surface. Moreover, the concentration of
OVs can be regulated by adjusting the treatment time, the
irradiation particle, and the intrinsic structure of the
metal oxide. For instance, Xu et al. [62] designed an OVs-
rich Co3O4 via a one-step plasma-engraving strategy. The
Co3O4 nanosheets array were treated by Ar plasma
(commercial 13.56 MHz RF source, 100 W power and
40 Pa pressure) with treatment time varying from 0 to 60,
120, 180, and 240 s. Gratifyingly, the Co3O4 engraved for
120 s contained a suitable amount of OVs and displayed
the highest catalytic performance. It must be noted that
not all high-energy particles are effective for generating
OVs. Chen et al. [66] demonstrated that whereas Ar
plasma creates OVs in NiO/TiO2, O2 or CO2 plasma does
not work under identical condition. Kim and coworkers
[63] also proved that under the same dose of proton ir-
radiation, amorphous zinc tin oxide (α-ZTO), amorphous
indium gallium zinc oxide (α-IGZO), and crystalline zinc
oxide (ZnO) produced different concentrations of OVs,
and the concentration also differed when the dose of
proton irradiation varied (Fig. 2b–e).
3
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

centration of OVs obtained after calcination. Higher

temperature and extended heating time normally increase
fcln CGa WZn 4,Sn «0 the concentration of OVs [89,90]. For instance, Tan et al.
[91] found that SrTiO3 annealed at 375°C had higher
Proton Irradiation
concentration of OVs compared with the samples an-
nealed at 300°C, and extending the heating time from 30
to 60 min further assisted OVs formation. Likewise,
Jaiswar et al. [92] demonstrated that annealing CaMn7O12
Ct-IGZO
at 970°C created more OVs when the heating time was
increased from 12 to 15 h. Nevertheless, there are also
exceptions. For example, Jiang et al. [93] observed that
CX-ZTO the concentration of OVs in Co3O4 decreased when the
annealing temperature was increased from 350 to 700°C,
b ZnO c a-IGZO and reasoned that Co3O4 suffered from pyrolysis at high
.10- . -
M O -H
101scm ‘ 2
dose - -
M O H
15
cm - dose
2
temperature.
^ -co",H'
vSoa ° The effects of the atmosphere and pressure on the
1014cm 2
do 9 e
1014cm generation of OVs during calcinations are increasingly
2
3 dose 3
<n
& & 1013cm ‘2
appreciated in recent years. Hypoxic atmosphere (e.g.,
dose
(/
C
> 1013cm
2
dose </
c
)
vacuum [94–96], He [97], Ar [85], and N2 [98]) facilitates
Q> (1)

C c the formation of OVs. In case of annealing VO2 film in Ar

Reference
Reference atmosphere, Xu et al. [85] found that increasing the Ar
pressure generated a larger number of OVs, and also
534 532 530 528 534 532 530 528 observed a shift of the V 2p3/2 peak to a lower binding
Binding Energy ( eV ) Binding Energy ( eV )
energy. Vacuum tends to create more OVs at a relatively
d ct-ZTO ( 2:1) e a-ZTO (4:1) low temperature [96,97,99,100]. Liu et al. [96] found that
—
_ -- .- -
M O H
cm - dose
,
4
10
« 15 2 M O »< M
M -O -M the amount of OVs in the annealed SnO2−x/In2O3−y in-
creased when the annealing was carried out in an ultra-
3
10 ucm ’2
dose high vacuum (UHV) system instead of a furnace an-
nealing system (Fig. 3). In fact, a hypoxic atmosphere is
*
(/)
C
a)
1013cm ’2
dose desired but not mandatory. For example, Bao et al. [39]
demonstrated that annealing NiCo2O4 nanosheets in air
c
Reference
created OVs-rich NiCo hydroxides, and the amount of
OVs reduced sharply when the same process was carried
534 532 530 528 534 532 530 528
Binding Energy ( eV ) Binding Energy ( eV )
out in O2 atmosphere.

Figure 2 (a) Schematic of high-energy proton irradiation on oxide- Chemical reduction

semiconductor thin-film transistors (α-ZTO, α-IGZO, and ZnO); the O
1s spectra from X-ray photoelectron spectroscopy (XPS) analysis are
given for (b) ZnO, (c) α-IGZO, (d) α-ZTO (2:1), and (e) α-ZTO (4:1)
before and after various doses of proton irradiation. Adapted with
permission from Ref. [63], Copyright 2018, WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim.
Thermal treatment
Alternatively, calcination of samples at high temperature
in an oxygen-deficit atmosphere also creates OVs [84].
During calcination at high temperature, the surface atoms
vibrate violently, and the surface lattice oxygen can easily
diffuse and overflow [85–88].
Experimental parameters like heating temperature and
time generally play critical roles in tailoring the con-
Although the abovementioned methods efficiently create
OVs, they cannot activate the lattice oxygen at low tem-
perature, which hinders deliberate control in generating
OVs. In contrast, the chemical reduction of metal oxides
by chemical agents (e.g., H2 [31], NH3 [101], NaBH4
[102]) could produce OVs at relatively low temperature.
The reductive molecules are firstly adsorbed on the sur-
face of metal oxides, and then grab O atoms through
electron transfer to the surface oxygen and thus generate
OVs. Hydrogenation is currently the most popular
pathway in chemical reduction [101,103–105].
Ye et al. [59] found that the reductive H2 atmosphere
modulates the thermodynamics and the temperature re-
quired for creating OVs on In2O3. They showed with DFT

4 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

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Figure 4 Calculated reaction energy diagram of NH3 treatment over the
WO3 (001) plane, along with mass spectrometer signals (online MS
signals) of N2, NO, H2O, and N2O generated from the temperature-
r

programmed reaction of WO3 with NH3. Adapted with permission from

Ref. [101], Copyright 2019, Elsevier.

gously, Wang et al. [110] presented a universal low-

Figure 3 Schematic and structure of SnO2−x/In2O3−y prepared from
UHV (solid) and furnace annealing (dotted) system, with O atom in
blue. Adapted with permission from Ref. [96], Copyright 2018, Elsevier.
calculations that a redox reaction between H2 and the O
atoms of In2O3 to form H2O and OVs was intrinsically
exothermic, with the formation energy (EV) of OVs being
−0.57 eV (Table 1). In contrast, Bielz et al. [106] pre-
viously created OVs on In2O3 at ∼673 K by calcination,
but Ye et al. [59] could create OVs at a relatively lower
temperature of 340 K with the presence of H2. Note that
temperature also determines the concentration and type
of OVs. Zhu et al. [107–109] adopted H2 reduction to
control the concentration and type of OVs on the surface
of BiPO4−x. When the temperature is set below 270°C,
most OVs reside on the surface of BiPO4−x. The con-
centration of OVs gradually increases with rising tem-
perature, and over 300°C, both surface and bulk OVs are
created. The oxygen-deficient BiPO4−x with surface OVs
has higher photocatalytic activity than the BiPO4−x rich in
bulk OVs.
Ammonia (NH3) is another commonly used reducing
agent. Thanks to its weakly reducing reactivity, NH3 helps
create OVs in transition metal oxides (TMOs) during the
nitridation process. A possible mechanism was proposed
by Liu et al. [101], who demonstrated when WO3 was
treated with NH3, both the H and N atoms of NH3 can
seize O atoms from WO3, to form H2O, N2, N2O, and NO
and reduce WO3 to OVs-rich WO3−x (Fig. 4). Analo-
temperature ammonia reduction method to prepare OV-
enriched TMOs without N-doping. For example, they
prepared OVs-rich TiO2 by heating commercial P25-TiO2
in flowing NH3 [110,111]. Maqbool et al. [112] also cre-
ated black anatase TiO2 rich in OVs by NH3 reduction.
According to the diffuse reflectance UV-vis-NIR spec-
troscopy, the obtained OVs-rich TiO2 shows an absorp-
tion that not only covers visible light but also extends well
into the NIR. In contrast, the pristine TiO2 can only re-
spond to ultraviolet irradiation.
The reduction of metal oxides can also take place in the
liquid phase. The reduction in the liquid phase enables
large scale modification of oxides under mild condition,
and the OVs concentration can be readily manipulated by
adjusting the dose of reducing agent, the reaction tem-
perature, and time [113]. Thus far, OVs-rich Co3O4 [114],
Bi2WO6 [115], and Bi4MoO9 [102] have been prepared by
NaBH4 reduction at room temperature in the liquid
phase. Intriguingly, substantial OVs are created in
0
Bi4MoO9/Bi by only stirring the precursor in aqueous
NaBH4 [102]. Yang et al. [116] integrated perovskite
La0.8Sr0.2CoO3 (OM LSCO) catalysts that had an ordered
macroporous structure into commercial cordierite with-
out adhesives by in situ solution assembly and then cre-
ated OVs on the resulting material by NaBH4 reduction
to give OVs-OM LSCO (Fig. 5a). The presence of OVs is
clearly established by XPS and electron paramagnetic
resonance (EPR) (Fig. 5b–e). The OVs-OM LSCO has
significantly enhanced activity for low-temperature CO
oxidation because the ordered macroporous framework
endows the perovskite with a high degree of accessible
reactive surface and the engineered OVs notably im-

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 5
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

the long-term periodic order of the lattice oxygen in the

Impregnation
& drying oxide. For instance, OVs will be created to maintain the
3+
electrostatic balance when a low valence M dopant is
Bare ceramics with Colloidal crystal Template immersed into incorporated into MO2 [121–128]. The dopant ion with a
template on ceramics perovskite solution
LSCO seed layers
low valence state subsequently substitutes the original

b
OVs-OM LSCO OM LSCO
C Co 2p
Iw P '
实验掺杂
metal nodes in the oxide, and as a result, OVs are formed
to rebalance the charge. For example, OVs are needed
3+
when a La ion serves as a dopant to substitute Ce in
4+

CeO2 [129]. Similarly, Wang et al. [130] found that the

OVs -OM LSCO 0 1s
-OH orOa d s -
OVs OM LSCO Ni-doped La0.8Sr0.2Mn1−xNixO3 had more OVs than the
7
Defect f Adsorbed Co3+ undoped La0.8Sr0.2MnO3. Ion exchange is a facile means to
3 °
latt
moisture
7
3
TO
implement doping and thus regulate OVs. For instance,
.
C3
&
>
</i
OM LSCO C/)
c OM LSCO
OVs-rich NiO nanorods have been created from a ZnO
GJ 2+
C
G)
C
C precursor by ion exchange with Ni [131], and OVs-rich
CoO is also produced from ZnO by ion exchange with
2+
T
Co [132].
770 780 790 800 810
526 528 530 532
Binding energy ( eV)
534 536
Binding energy ( eV) Theoretical studies have been performed to reveal how
d OVS-OM LSCO e OVs-OM LSCO ln air atmosphere the dopants affect the formation of OVs. From DFT
OM LSCO OM LSCO S
\ calculations, Nolan et al. [61,98,129,133] suggested that
3
t

/
g = 2.001
3 Lj compared with the undoped counterparts, the doped
S
& &
a V
materials can produce OVs more easily because low va-
w
c
QJ
5 lence metal dopant led to a lower EV. The EV of rams-
jl
c
\
lj
> RT
dellite-MnO2 doped with Zn is −0.90 and −0.57 eV on the
In high vacuum 2.013 1.995
2.002
Oj '

2990 2995 3000 3005 3010
Magnetic Field ( G)
Figure 5 (a) Schematic illustration of the fabrication process of OVs-
OM LSCO; (b) O 1s and (c) Co 2p XPS spectra of OVs-OM LSCO and
OM LSCO; low-temperature EPR spectra of OVs-OM LSCO and OM
LSCO (d) in high vacuum and (e) in air. Adapted with permission from
Ref. [116], Copyright 2019, American Chemical Society.
proves the abundance of monatomic oxygen ions (O ).
OVs can also be created when the metal oxide is treated
in a weakly reducing alcohol solution [117,118]. Bai et al.
[119] introduced OVs to Bi5O7I nanosheets by stirring the
precursor in a mixed solvent containing ethylene glycol
and ethanol. The ethylene glycol is believed to reduce the
surface oxygen atoms of Bi5O7I because the oxygen
density is high on the (001) surface of Bi5O7I. Cai et al.
[120] successfully produced OVs on the (111) surface of
Co3O4 via the solvothermal reduction of Co3O4 in ethy-
lene glycol under alkaline condition. In general, the ad-
vantages of solution or solvent-based strategies include
room-temperature processing, shorter reaction time,
controllability, versatility, and scalability.
Ion doping
As a conventional tool to tune the chemical composition
and properties of functional materials, ion doping also
could produce OVs because the dopant always destroys
^O
77 K
' + Oj
(110) and (010) surfaces, much lower than that of the
3275 3280 undoped ramsdellite-MnO2 (0.22 and 0.76 eV respec-
Magnetic Field ( G)
tively) [134]. Wang et al. [133] also found that the first
2+
OV formed in Cu -doped CeO2 was spontaneous thanks
to the charge compensation. The presence of first OV
then expedited the formation of the second and third
OVs, and the EV reduced from 1.82 eV for the first OV to
1.65 eV for the third OV (Fig. 6). These OVs tend to be
−
generated near the Cu sites, indicating that the O atom
adjacent to the doped cation is more labile to overflow
[135].
Apart from cation doping, anion doping (e.g., with N,
C, and S) may also contribute to the formation of OVs
[9,136–139]. For instance, Li et al. [140] designed OVs-
rich Co3O4 and CoO by doping P anions via controlled
calcination of cobalt–alanine complexes. Sun et al. [141]
used gaseous sulfur treatment to create OVs on the sur-
face of Li1.2Ni0.13Co0.13Mn0.54O2 (LNCMO@S) uniformly
by replacing oxygen with S atoms (Fig. 7). Instead of
resorting to conventional calcination, Sun et al. [142]
adopted a facile ionic liquid strategy to dope N, P, and F
into CoFe2O to create abundant OVs. Unfortunately,
compared with cation doping, the mechanism of gen-
erating OVs by anion doping is much less investigated.
Interfacial engineering
Adjusting the heterostructure interface further assists
异质结构

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interfacial region was disordered and contained low co-

ordinated Ti sites and abundant OVs. Qiu et al. [149]
designed a built-in p–n heterojunction that combined
catalytically inactive CeO2 with Co3O4 to construct CeO2/

CuCe,. , .,
°2x
?$&$? CuCex,02xJ
Co3O4 (Fig. 8a). Substantial OVs are formed by the
strongly coupled heterojunction interface according to
XPS (Fig. 8c–f), and they allow rapid interfacial charge
transfer from CeO2 to Co3O4 (Fig. 8b), which improves
Surface O
the catalytic performance of the heterojunction. Veal et
O V0

• Sub-surface O O Cu
C
- al. [150] distributed OVs in In2O3/ZrO2/Y2O3 hetero-
structured oxides with reversible control of the OVs
O Surface Ce concentration. The redistribution of oxygen ions across
the heterointerface is induced by an applied electric field
Sub-surface Ce
oriented in the plane of the interface.

/
a r
CljCex 102xJ ;•-
my - Calcination as
Figure 6 Theoretical calculations of the most stable structures and EV of
CeO2 (110) doped with one single Cu site with (a) 1 OV; (b) 2 OVs; and w Crystallization

(c) 3 OVs. Adapted with permission from Ref. [133], Copyright 2018,
American Chemical Society.
*
Ce(OH) /Co(OH) , Ce0 j/C0 j04\ •ROTi
nanowires nanotubes nanotubes \
LNCMO LNCMO @S

Sulfate

r
Gaseous Sulfur

NiCoMnLi
o c Co 3d
:55
4 » Wr
d
Ce ?
c 2
4* 5
CeO? T3
=
Figure 7 Creating OVs by the partial replacement of O by S via anion =!
n <o

doping after gaseous sulfur treatment of Li1.2Ni0.13Co0.13Mn0.54O2 >•

Ce
J% e
3* i >•
V -
(LNCMO). Adapted with permission from Ref. [141], Copyright 2019, c A -o 2 c« A £
c
£
Elsevier. Cc 02 / Co304 CeO? / Co 304
920 915 910 905 900 895 890 885 880 540 538 536 534 532 530 528 526
Binding Energy ( eV ) Binding Energy ( eV )
OVs formation [143–145]. Lately, Nolan et al. [146,147]
e Co 2p ± Co 2PI /2
C 2PW
f -
found that the formation of point defects such as OVs ° Co L edge
i Co3* ( Oh)

was significantly more favorable in the heterojunction of Sat. "C Mfo 3

Co^*( Tfl&Oh)^ .-
/ , erlge
CO3O4 O
. -cdge

——“^°
mixed-phase TiO2 than in single-phase TiO2. Along with c ’(TdK
2 {

£
c
£ CO 2PI/2 A *g C / COjoJ
newly added OVs, electrons are localized into low co- £
C
&
PoA
£
£
A |
ordinated Ti sites in the interfaces, thus creating special Cc02 / Co3 ° 4

active sites in mixed-phase TiO2. Abundant OVs are often 810 805 800 795 790 785 780 775 760 768 776 784 792 800

found close to grain boundaries or heterojuctions [19], Binding Energy ( eV ) Photo Energy ( oV )

because the EV is always dependent on the position
[146,148]. For example, the LaAlO3/SrTiO3 interface has
much smaller EV than the surface of LaAlO3 [148]. Fo-
cusing on polytype TiO2, Nolan et al. [146] performed
泛密度理论
DFT calculations to probe the effect of the rutile–anatase
TiO2 interface on defect formation. They found that the
Figure 8 (a) Illustration of the fabrication process of CeO2/Co3O4 hy-
brid nanostructure; (b) model and charge-density difference of the CeO2
(111)/Co3O4(110) interface; (c) Ce 3d XPS of CeO2 and CeO2/Co3O4; (d)
O 1s and (e) Co 2p XPS spectra of Co3O4 and CeO2/Co3O4; (f) Co L-edge
X-ray absorption near-edge structure (XANES) of Co3O4 and CeO2/
Co3O4. Adapted with permission from Ref. [149], Copyright 2019,
American Chemical Society.

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Substantial OVs are also found in Pt/TiO2 [151], Pd/ a 8

0 LCr
CeO2 [152], Cu/CeO2 [153], and Ag/MnO2 [143] at the >Q Insulators &
)
/
interface between the pure metal and the oxide matrix.
Qu et al. [143] found that Ag promoted the formation of
+
OVs in MnOx. Presumably, Ag species are generated at
>
ao 6
0)
c
Q)
Semiconductors /
2
R =0.94 ,' SrT 03
A
/O
. OLM
OLF
LCo
o/ OLN
interface, which enhances the interaction between Ag and I4 O'
Bond strength LSCr 64
Mn species, and more OVs then develop on the Ag-em- to
E r and AE increase • LSM 64
bedded MnOx. Gac et al. [154] demonstrated with tem- o 2 o • LSF64
perature-programmed desorption (TPD) and o LSC064
Metallic oxides
temperature-programmed reduction (TPR) analysis that 0 • LSN 64
Ag can increase the oxygen mobility of MnOx at low 2 3 4 5 6
temperature to benefit the formation of OVs. By calcu- - AHFfEQRxfde [eV/atom] +0.26 * AEDFT +U [eV]
lating the atomic and electronic structure of the CeO2 b 8
(111) surface in the presence and absence of Pd, Yang et >
al. [152] reported that the EV at the Pd/CeO2 (111) in- m Insulators & ,' o MgO
> Semiconductors *
terface was about 0.4–0.8 eV lower than at the CeO2 (111) t»o 6
0) R2 =0.94 :SrTiOj
surface. c
o

Theoretical studies on the formation of OVs •

To determine the relationship between the structure and
properties of the materials at atomic level, it is indis-
pensable to examine the thermodynamics and kinetics of
OVs formation by theoretical analysis [155,156]. It has
been generally accepted that the formation of OVs in-
volves of the destruction of the M–O bonds of the metal
oxide. Hence, the EV is normally found to be highly de-
pendent on the M–O bond of the metal oxide. Michalsky
et al. [157] found by DFT that the EV on the surface of the
metal oxide correlated with the free energy of formation
of the bulk metal oxide (i.e., Gbulk oxide), and a lower
Gbulk oxide corresponded to lower EV on the surface of the
metal oxide. Deml et al. [61] also performed DFT cal-
culations of perovskite oxides of different transition me-
tals and found their EV falling in order of LaCrO3 >
LaFeO3 > LaMnO3 > LaCoO3 > LaNiO3 (Fig. 9). In fact,
the EV is closely related to the formation enthalpies of the
metal oxide, an indicator of the average M–O bond
strength. Hence, it can be expected that the formation of
OVs depends greatly on the structure of the metal oxide,
including phase, crystal plane, crystallinity, and strain.
Oxides with same chemical component frequently have
different phase states. For example, Hara et al. [158–161]
found phase-dependent EV of MnO2 falling in the order
of α-MnO2 > γ-MnO2 > λ-MnO2 > β-MnO2, which was
the exact inverse order of their oxidative power (Fig. 10).
This is consistent with theory and experiment, where a
lower EV indicates a better oxidant. In a related study,
Hayashi et al. [158] revealed from DFT calculations how
EV varied for different types of MnO2 with distinct
structure and bearing disparate types of constituent
o
— ^ P’
E
5 2 o
o
0
• Metallic oxides
2 3 4 5 6
- AH oxpt
oxide [ eV / atom ] + 0.25 * AE 6 Xpt [ eV ]
f ,
Figure 9 EV for LaBO3 (LB) and La1−xSrxBO3 (LSB) of varying compo-
sitions as a function of the linear combination of (a) calculated and (b)
experimental band gap energy (ΔE) and formation enthalpy (ΔHf, oxide)
of the oxide. Adapted with permission from Ref. [61], Copyright 2014,
The Royal Society of Chemistry.
oxygen atoms. Specifically, β-MnO2 consists of planar μ3-
oxygen atoms and thus has a lower EV (3.25 eV), whereas
λ-MnO2 only has bent μ3-oxygen atoms and the corre-
sponding EV is higher (3.44 eV). In sharp contrast, α-
MnO2 and γ-MnO2 contain both types of oxygen atoms
and thus have two EV values (bent, 3.25 and 3.15 eV;
planar, 3.95 and 3.84 eV, respectively). From the struc-
tural point of view, EV is generally lower at the bent
oxygen site than at the planar oxygen site. The exception
is β-MnO2, for which the planar oxygen site has a lower
EV.
Crystal planes possess different EV if they have distinct
chemical composition or surface geometry [162–164]. Xie
et al. [165] demonstrated that compared with the (002)
plane, the (111) plane of CeO2 was more compact and less
prone to accommodate OVs. Li et al. [162] pointed out
that the BiOCl (010) surface can host OVs more easily
than the BiOCl (001) surface because the former had an
open channel structure. Tompsett et al. [166] system-

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O atoms have weaker lattice constraint and charge loca-

lization [168]. In fact, OVs are readily found in amor-
phous materials, such as SnO2 [169], CoOx [170], etc.
Duan et al. [171] found that amorphous NiFeMo oxide
formed abundant OVs after oxygen evolution reaction
(OER), but fewer OVs were formed for the crystalline
(3- MnOo y- Mn02 A-Mn02 NiFeMo oxide. They speculated that the amorphous Ni-
FeMo oxide possibly allowed more rapid diffusion and
Ho
^yr^°
HMF
A
reconstruction of metal ions, giving rise to a lower EV.
Nanostructured materials are appealing precursors of
*
OVs-rich catalysts due to their relatively large surface
4 ^~
i
area and good exposure of coordinated atoms, both fa-
HO O
CD
cilitating the generation of OVs [172,173]. As an ex-
2
emplary 2D nanomaterial, ultrathin Bi2MoO6 nanosheets
show higher OVs concentration and better performance
FDCA
Y -Mn02 a- 2 in the photocatalytic degradation of phenol when com-
> pared with bulk Bi2MoO6 [174]. Similarly, the activity of
Vacancy formation energy
BiOCl in the degradation of RhB was found to be closely
Figure 10 (a) Structural model of different MnO2 phases; (b) the re- related to the thickness of BiOCl: the thinnest BiOCl
lationship between reactivity and EV of different MnO2 phases. Adapted nanosheet had the highest amount of OVs and the best
with permission from Ref. [158], Copyright 2019, American Chemical
Society. catalytic activity [175]. In the case of 1D nanomaterials,
Liao et al. [176] found that the OVs concentration of ZnO
atically investigated β-MnO2 with regard to surface nanorods increased when the diameter was lower. A size-
chemistry and catalytic performance. According to DFT dependent variation of OVs concentration was also found
calculations, crystal planes with varying degrees of ex- in CeO2: the OVs concentration in CeO2 was decreased
20 −3 18 −3
posure have different EV [167]. For β-MnO2, the (311) from 4×10 cm (1.7%) to 7.2×10 cm (0.028%) as the
plane has the lowest EV of 0.96 eV, and the (001) plane crystal size increased from 4.6 to 60 nm [177].
has the highest EV of 1.43 eV (Table 2). Higher surface It must also be noted that crystal strain (compressive or
energy is more likely to result in higher EV. In fact, the tensile) also affects OVs formation. Petrie et al. [178]
surface energy is 1.08 eV for the (311) plane and 1.80 eV calculated the EV of the SrCoOx with varying strain and
for the (001) plane. Moreover, OVs are more inclined to found that the formation of OVs was determined by the
form on the surface than in the bulk. compressive strain but aided by the tensile strain, because
The crystallinity of the material also affects EV. Amor- the tensile strain weakened the Co–O bond and gave a
phous materials are more prone to form defects than lower EV (Fig. 11). However, in the case of OVs in thin
long-range ordered crystalline materials. Amorphous SrTiO3 films, Iglesias et al. [179] concluded that com-
metal oxides lack highly ordered arrangement in the pressive strain reduced EV and was beneficial for the
three-dimensional (3D) space, and both the metal and the formation of OVs.
Characteristics of different strategies are summarized in
Table 2 EV for different crystal planes of β-MnO2. Adapted with Table 3, availing researchers to choose an appropriate
permission from Ref. [166], Copyright 2014, American Chemical So- strategy.
ciety.
Miller index EV (eV) CHARACTERIZATIONS OF OVs
(100) 1.13 Advanced techniques for material characterization are
(101) 1.26 required for elucidating the mechanistic features of OVs
(001) 1.43 in catalytic reactions. Several techniques are suitable for
(110) 0.98 identifying OVs, including XPS, EPR, UV-vis diffuse re-
(211) 1.09
flectance spectra (UV-vis DRS), thermal gravimetric
analyzer (TG), and temperature-programmed desorption
(311) 0.96
(TPD-MS), X-ray absorption fine structure spectroscopy
Bulk 2.26
(XAFS), scanning tunneling microscopy (STM), and DFT

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a
100
o2- QPtetrahedral
9 9
L010 saddle

* /

100 02 (intercalated) O2 (saddle)

u
‘ '

9 9
010 -e
b 1.0 c
8= -2%
0.8
0.8
/ \

>
CD
^« 0.4
0.6
/tV
• * g = 0%
s \
?
CD
0.6

Uj CD
iS 0.4
0.2

0.0 0.2

0.0 0.2 0.4 0.6 0.8 1.0 -2 -1 0 1 2

Reaction coordinate (unit cell) Strain (%)
Figure 11 (a) The path and energy barriers (Ea) for oxygen ion movement in brownmillerite phase SrCoOx through OVs channels when the oxide
undergoes a topotactic oxidation to form perovskite phase SrCoOx; (b) as an oxygen ion moves from one intercalation site to another along the [010]
direction of the OVs channel, the Ea increases as the strain rate tends from +2% to −2%, where higher Ea is more difficult for OVs to form; (c) a
summary of the intercalation enthalpy (Hi) and the activation energy (ΔEa) as a function of strain. Adapted with permission from Ref. [178],
Copyright 2016, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Table 3 Advantages and shortcomings of developed synthetic strategies for OVs

Required atmosphere or re-
Synthetic strategy Temperature agent Controllability Structural damage

Atmosphere
High-energy particle Ambient Ar/Xe/He… Time Minimal
bombardment
Pressure
Temperature
Time
Thermal treatment High He/N2/Ar/air/vacuum Slightly
Atmosphere
Pressure
Reducibility Slightly, but may incurphase
Chemical reduction Ambient H2/NH3/reducing regents
Time transformation
Type of dopant ion Introduce dopant, and may in-
Ion doping Ambient Dopants
Concentration of dopant ion cur phase transformation
Type of noble metal
Interfacial engineering Ambient Not required Type of transition metal oxides New hybrid structure
Heterostructure

modeling [180–183]. oxygen atoms of distinct states. In general, the peak at

XPS is a facile method to examine the oxidation state of 529.3–530.5 eV represents oxygen in the lattice, the peak
elements on the surface of metal oxides [184]. It gives the at 530.5–531.7 eV can be ascribed to the adsorbed oxygen
O 1s spectra of oxides, which can frequently be decon- on OVs, and the band at 531.8–532.8 eV corresponds to
voluted into two or three distinct peaks corresponding to adsorbed H2O on the oxide. The relative OVs con-

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 SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS
centration can be estimated by dividing the area of the
OVs peak to the area of the whole O 1s or the lattice
oxygen peak. Liao et al. [176] disclosed that the OVs
concentration of ZnO depended on the time when it was
treated with H2 plasma: 57% for 30 s and 76% for 60 s,
and that the ZnO rich in OVs gave higher catalytic per-
formance for CO2 reduction. In addition, XPS also shows
the oxidation state of metals in the oxides. Generally,
3+ 2+
when low valence ions like M or M exist in MO2, VOs
are created to maintain the electrostatic balance [185–
187]. For example, Jiang et al. [93] synthesized a series of
Co3O4 by varying the temperatures at 300, 500, and
2+ 3+
700°C. The Co /Co ratio of the Co3O4 falls in the order
of 300°C (1.30) > 500°C (1.05) > 700°C (0.78), and the
peak area ratio of OVs/whole O 1s falls in the order of
300°C (0.35) > 500°C (0.25) > 700°C (0.18). Therefore,
more OVs are generated at lower temperature.
EPR is a common technique to assess unpaired elec-
trons. A characteristic EPR signal around g = 2.004 is
俘获
related to electron trapping at OVs. Fan et al. [188] found
that the EPR signal at g = 2.004 had higher intensity for
OVs-rich BiOI nanosheets than perfect BiOI. Xie et al.
[189] proved that Au nanoparticles promoted the for-
mation of OVs on TiO2 nanorods annealed in H2. The
intensity of the EPR signal at g = 2.004 falls in the order of
Au/TiO2/H2 > TiO2/H2 > pristine TiO2.
UV-vis DRS, TG, and TPD-MS also provide useful
clues regarding OVs. For instance, Guo et al. [190] doped
CeO2 with rare earth metal, and the resulting material
showed enhanced light absorption at 255 nm compared
with pure CeO2 thanks to the presence of OVs. TG can
reveal whether OVs are refilled with oxygen, which
readily occured at high temperature. For instance, at
>260°C, bulk Bi2MoO6 displays drastic weight loss but
ultrathin Bi2MoO6 nanosheets rich in OVs have a much
lower weight loss [174]. Zhu et al. [191] demonstrated
with TPD-MS how the O atom in MnO2 lattice over-
flowed to create O2 and OVs during calcination. Raman
spectroscopy provides information related to chemical
bonds and structural characteristics. Jin et al. [192,193]
found that the intensity of characteristic peaks of ZnO at
−1
332, 379 and 437 cm weakens in the presence of
abundant OVs.
OVs may give rise to a low oxygen coordination
number of oxides, and XAFS is a powerful tool to de-
termine the local atomic arrangements of metal oxides.
For instance, Zhang et al. [194] fitted the WL3-Edge
EXAFS and found that the oxygen coordination number
of W was lower in OV-rich WO3 (5.4) than in com-
mercial WO3 (6). Zhao et al. [60] studied how Cu doping
© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
affected the TiO2 OVs during photocatalytic N2 fixation.
They found from XAFS spectra data a decrease in both
the intensity of the Ti–O shell peak and the Ti co-
ordination number in TiO2 when the amount of Cu do-
pant escalated from 0% to 6%. After further calculation,
the OVs concentration of 0%, 1%, 3%, and 6% Cu-doping
TiO2 was found to be 0.985%, 1.845%, 2.195% and
8.621%, respectively. Tan et al. [195] also inferred from
the XAFS result of NiAl-LDH with different thickness
that the OVs concentration of monolayer and few layers
−3
NiAl-LDH was 1.80 and 2.14 nm , respectively.
STM images reveal the local atomic arrangement of the
oxide surface and hence show in a very straightforward
manner of the absence of O atoms in lattice. Feng et al.
[196] used STM to simulate the electrocatalytic hydrogen
evolution reaction (HER) process and found that OVs
acted as active sites to absorb and dissociate water during
catalysis. In monitoring the CO oxidation on Au/CuO
surface, Zhou et al. [104] found dark features in the STM
image of the Au/CuO surface that corresponded to the
presence of OVs due to the release of lattice oxygen.
These OVs disappear after Au/CuO is treated at 400 K in
O2. Esch et al. [197] applied STM to measure the OVs
concentration in CeO2 and suggested that the con-
centration of surface and subsurface OVs was 1.5% and
1.3% of the surface atoms, respectively.
DFT is a powerful method that constructs theoretical
models at atomic and molecular level to analyze changes
in electronic structure and assess catalytic mechanism of
materials bearing OVs. DFT calculations help estimate
bandgap changes [198], charge separation [55], as well as
adsorption and activation of substance involving in cat-
alytic reactions [199,200]. The energy barrier for the rate
limiting step of a catalytic reaction can also be calculated
to evaluate how OVs impact the efficiency and selectivity
of the catalysis [198]. Zhang et al. [198] demonstrated
with DFT calculation that OVs narrowed the bandgap of
CeO2 and can enhance optical absorption to facilitate
photocatalytic water oxidation. Huo et al. [55] found that
OVs on the Bi2WO6 surface had lower adsorption energy
for O2, and the O–O bond length of O2 adsorbed at OVs
was longer than at the perfect surface. The findings cor-
respond to efficient photocatalytic NO oxidation by O2
on the OVs surface.
MATERIAL PROPERTIES OF METAL
OXIDES THAT ARE ADJUSTED BY
MANIPULATING OVs
Current photocatalysts often suffer from low photo-
conversion efficiency and catalytic selectivity because of
11
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials
their limited light absorption capacity, inadequate reac-
tion kinetics, undesirable electron conductivity, etc., and
thus fail to meet the demands of practical applications
[201–204]. The OVs in metal oxides play a key role in the
mechanism and kinetics of the redox reactions mediated
by the metal oxides [149], and have been employed to
tune the catalytic performance of TiO2 [1,7,205], CeO2
[206], ZnO [7,85,207,208], CuO [12,13,209]. In fact,
tuning OVs can help improve multiple aspects of the
photocatalytic process simultaneously, including light
absorption [44,50], charge transfer and separation
[49,210], and surface reaction [211,212]. Similarly, reg-
ulating OVs to improve catalytic activity is also com-
monly used in electrocatalysis and thermal catalysis [213–
216]. Understanding the principles of action hence not
only helps understand how OVs affect the material
properties but also guides the design of catalysts with high
activity and selectivity. In this section, we approach the
effects of OVs on the material properties of the photo-
catalyst from several aspects, including examples from
electrocatalysis and thermal catalysis.
Band structure
Effective capture of solar irradiation is essential for
semiconductor photocatalysts, yet oxide-based photo-
catalysts normally have a wide band gap (>3.0 eV) that
can only respond to UV light (<315 nm). Regulating the
band structure of photocatalysts to improve their ability
to harvest solar energy has been a challenge. Substantial
evidence has been reported over the past decades on how
OVs improve the ability of photocatalysts to absorb
visible light [217] (e.g., CeO2 [218], ZrO2 [219,220],
Ga2O3 [221], BiOBr [222], BiOCl [223], BiVO4 [55], Bi-
FeO3 [224], BiPO4 [224], Bi2WO6 [223], TiO2 [148,105]).
New defect levels created by OVs render either a down-
shift of the conduction band (CB) minimum or an upshift
of the valence band (VB) maximum, and the narrowed
band gap then allows electron excitation by visible light
[64,225] or even NIR irradiation [124].
The VB maximum tail is extended when the new defect
level that originates from OVs overlaps with the VB
maximum [107,123,226–228]. In studying hydrogenated
TiO2 (H2-500) [226], Lv et al. [107] found that the OVs-
rich TiO2 absorbed visible light and estimated a slightly
upward shift of the VB maximum edge from the UV-vis
DRS and XPS VB spectra (Fig. 12a–c). Lv et al. demon-
strated an improved absorbance of OVs-rich BiPO4−x in
300–800 nm due to the broadened VB. Geng et al. [227]
performed DFT calculations to describe how OVs tuned
the band gap of the ZnO slab (Fig. 12d, e). A new defect
12 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
level appears near the VB maximum of the OVs-rich ZnO
slab, and electrons tend to accumulate around the defect
energy level, which reduces the transition energy of ex-
cited electrons. Except for the effect on the VB, OVs may
also form a donor level or localized electron states near
the CB. Ansari et al. [228] gave conclusions different to
those of Zeng in studying ZnO (Fig. 12f, g). They pre-
pared ZnO with OVs (m-ZnO), whose CB overlaped with
the defect level of OVs and was lowered distinctly. In fact,
the defect level of OVs may also form between the VB
and CB as an intermediate level, as is the case in OVs-
BiVO4, in which Feng et al. [229] revealed from DFT an
interband state between VB and CB (Fig. 12h).
Upon visible light irradiation, the defect level can ac-
cept electrons excited from the VB [19], and electrons in
the defect level also can be excited to the CB [230]. Lei et
al. [231] disclosed the presence of a defect level in the
band gap of oxygen-deficient In2O3, where electrons can
not only enter the defect level from the VB but also be
further excited from the defect level to the CB. All these
processes allow excitation of electrons by visible light.
Similarly, Wang et al. [230] proved the existence of an
intermediate level between the CB and VB of OVs-rich
BiOCl and demonstrated the electron transition from VB
to CB via the intermediate level under visible light irra-
diation (Fig. 12i). Yu et al. [232] modulated the con-
centration of OVs in Sr2Bi2Nb2TiO12 nanosheets (SBNT-
HR) for the fine and continuous control of the band gap
from 3.28 to 2.41, 2.28, and 2.11 eV, respectively (Fig. 13).
After creation of OVs, the photoresponse of Sr2Bi2Nb2-
TiO12 is extended from the UV to the visible region, and
its CO2 photoreduction activity increases to about 58
times that of its bulk.
Transfer of electrons
Electron transfer is generally considered as a critical step
in the catalytic reaction of CO2. Hence, it is indispensable
to develop approaches to engineer the electronic prop-
erties of catalysts, for which OVs provide a facile strategy.
The critical roles of OVs in promoting charge transfer
have been well documented [233–237]. It has been shown
that OVs can inhibit the recombination of photogenic
electron-holes because photo-induced conduction elec-
trons preferentially enter OVs rather than recombining
with holes [227,238]. For example, Sun et al. [239] de-
monstrated the high efficiency of OVs-enriched BiOIO3
0
in removing Hg and proposed, based on XPS and FT-IR
characterizations, that the OVs acted as positive charge
centers to trap electrons and thus inhibited the re-
combination of photo electron-hole pairs. Magyari-Köpe
SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

2m
*0

a
©
a

3<
B
o
. 3s.

09
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x
"a

r1
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3
z
..

5
PP
% s s
iahv)

3.16 eV

2.91 eV
f e

a
T
a-

£ 3
h* !**

d
3
6.

= -

I-
» *
o

o
ao o

O
90
K>

x
^
3"
S*
C

^I
DOS (state wot ’ eV ’)
O
A
O
OJ g
.Intensity (a.u )

Intensity ( a . u.)
O
N>
©
s i
DOS (state vor’ eV1)
Du
A
tO
D

o
-
-

-
-

°
S

a. s
ro S
o

»
B

-
JO
o»

S<T>' a

k
—
O'

K»

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c
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-
V

6
=
Figure 12 (a) UV-vis DRS of TiO2 treated by air (Air-500) and H2 (H2-500) to determine the optical band gaps, with the corresponding Tauc plots in
the inset; (b) XPS valence band spectra and (c) energy band diagrams of the Air-500 and H2-500 TiO2. Adapted with permission from Ref. [226],
Copyright 2018, Elsevier; calculated density of states (DOS) and partial charge density around the VB of (d) ZnO and (e) ZnO with an OV (gray, Zn;
red, O; white, H atoms; yellow regions, charge density contour). Adapted with permission from Ref. [227], Copyright 2018, Wiley-VCH Verlag GmbH
& Co. KGaA, Weinheim; (f) the density of electronic states for OVs-free ZnO (p-ZnO) and m-ZnO; (g) XPS valence band spectra of p-ZnO and m-
ZnO; the inset shows the zoomed valence band spectra. Adapted with permission from Ref. [228], Copyright 2013, The Royal Society of Chemistry;
(h) the OVs induce n-type doping mechanism under illumination. Adapted with permission from Ref. [229], Copyright 2019, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim; (i) mechanism of plasmonic photocatalysis on Bi/BiOCl. Adapted with permission from Ref. [230], Copyright 2017,
Elsevier.

et al. [240] also found that an OVs-rich filament induced OVs. From the molecular orbital (MO) theory and
several defect states within the band gap of TiO2, which Cambridge Sequential Total Energy Package (CASTEP)
subsequently led to defect-assisted electron transport. method, Gan et al. [251] suggested that excessive OVs on
In addition, accumulation of electrons around the VB the In2O3 can form an impurity band with unlocalized
maximum or CB minimum often promotes charge se- MO to trap electrons excited from VB to CB (Fig. 14a–c).
paration as well. From DFT calculations, Geng et al. [227] Indeed, the incident photon-to-current efficiency (IPCE)
found that the presence of OVs increased the charge is only 35% for In2O3 when there is an excessive amount
density of ZnO around the VB maximum, which en- of OVs but reaches 70% when the amount of OVs is kept
hanced the activation of CO2. In addition, OVs are also moderate. Li et al. [252] also obtained a similar conclu-
electron donors that improve the electronic conductivity sion in calculating the electronic structure of β-MnO2
of the catalyst [109,241]. For instance, thanks to the with DFT+U and showed that excessive OVs began to
presence of the OVs, the electron transport layer of OVs- weaken the charge density on the (110) crystal plane
rich TiO2 possesses high electron density and electrical (Fig. 14d,e).
conductivity [242]. This phenomenon is not restricted to
TiO2 but found in many other metal oxides as well, in- Adsorption and activation of molecules
cluding VO2 [243], Sr2FeMoO6 [244], TiO2 [72,245], The adsorption and activation of substrate molecules can
Cu2O [246], BiOIO3 [239], BaCeO3 [247], BiOCl also be enhanced by preparing OVs-rich catalysts and
[248,249], α-Fe2O3 [250], etc. introducing oxygen-deficient and electron-rich surface
It must be noted that excessive OVs may end up states [248,253–258]. Upon contact, the OVs-rich catalyst
trapping electrons and restraining electron mobility changes the state of the reactant (e.g., bond length, bond
[251], which is probably why catalyst with abundant OVs angle, coordination mode or intermediates) [259–264].
sometimes gives weak photocurrent density and low The deficiency of oxygen in the lattice increases the
catalytic performance compared with catalyst with fewer amount of uncoordinated active sites, and thus improves

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 13
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

study on the adsorption and dissociation of molecular O2

both at the bridge-bonded OVs (BBOVs) and at the hy-
−
droxyls (OH ) on the TiO2 (110) surface. Whereas the
singly adsorbed molecular O2 at BBOVs is activated and
can be dissociated via an intermediate state driven by the
STM tip, the singly adsorbed molecular O2 at the hy-
. .
• Sr
V SrU

" droxyls survives the tip-induced effect. Zhang et al. [273]

•
NOTI
0

designed OVs-abundant InOx and verified that the OVs

g
f .0
—
—
-
SBNT SSR
SBMT 44
SBMTMR OJ*- -_ itMIMI
JW W
'
*NT«R « >
-SBNT.HRU. «v I
-
S8NT SSR
.
S8NI HR
improved the catalytic activity of InOx in CO2 electro-
= 0.8 !
- -
SBKT MR OS
- -
SBNT MR 1
*S. * 1
1
?} -
SBNT HR-0.3
reduction by changing the coordination environment of
5.
3 SBNT-HR-O.S
M1 V
,1
0) 0.6 . ? » «»
re . - -
SBNT HR 1
CO2. In the temperature-programmed desorption of CO2
u J
2*
hv («V) *
Jo. 4 (/)
C
re
g=2.001
II
i
(CO2-TPD), OVs-abundant InOx has two different tem-
w 0.2 c
peratures for the chemical desorption of CO2 (389.3 and
< 0.0
413.9°C), but OVs-poor InOx has only one (364.7°C),
300 400 500 600 700 800 322.2 322.8 323.4 324.0 324.6
Wavelength (nm) Magnentic Field (mT) indicating that OVs improve the chemisorption ability
ih and capacity of InOx for CO2.
h Nd 3d Ti 2p O 1s
i
SBNT HR 1 - - - -
SBNT HR 1 Theoretical calculations help describe the relevant
SBNT -HRjyj* - -
SBNT HR 0.5 structural changes of substrates at the molecular and
3
re
2
co
SBNT -HR-0.
*A -
^ 3
re
2
.
</>
SBNTHR 0.3 - atomic level. In general, OVs activate reactants by
weakening the chemical bond or changing the bond an-
c
S A SBNT HR - A c
re SBNT -HR
c
£ SBNT -SSR/Jw
-
SBNT SSR
gle. Yu et al. [232,267] found that OVs-rich Sr2Bi2Nb2-
A

TiO12 required a much lower adsorption energy

204 207 210 455
Binding Energy (eV)
Figure 13 (a) Crystal structure of Sr2Bi2Nb2TiO12 nanosheets (SBNT-
HR) without OVs; (b) TEM image and (c) SAED pattern of SBNT-HR-
0.5 (SBNT-HR treated with 0.5 mL glyoxal to create OVs); (d) HRTEM
image of SBNT-HR; (e) HRTEM image of SBNT-HR-0.5; the OVs
concentration of the bulk (SBNT-SSR), the perfect nanosheets (SBNT-
HR), and the defective nanosheets (SBNT-HR-X, X denoting the amount
of glyoxal used to treat SBNT-HR to create OVs, X = 0.3, 0.5, and 1 mL)
are determined by (f) UV-vis DRS (band gap shown in inset), (g) EPR,
(h) Nd 3d, Ti 2p, and (i) O 1s XPS. Adapted with permission from Ref.
[232], Copyright 2019, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim.
the affinity of the oxides toward ions or molecules. For
instance, Zhang et al. [211] reported extremely high ad-
sorption affinities of OVs-rich WOx/C nanowire toward
2+ −1 −1
Pb (1224.7 mg g ) and methylene blue (1188.3 mg g ).
Similarly, OVs confined in ultrathin NiCo2O4 nanosheets
lower the energy barrier for the adsorption of H2O and
improve the OER efficiency [39].
With regard to the reactant, the OVs as electron cap-
ture sites can modulate both the coordination structure
and the electronic states of the adsorbed reactant, thereby
facilitating the activation of molecules [116,232,258,265–
271]. For instance, Li et al. [248] showed in the case of
Au-supported OVs-rich BiOCl, the OVs on BiOCl can
facilitate the trapping and transfer of plasmonic hot
−
electrons to the adsorbed O2 to produce ·O2 . Tan et al.
[272] performed a scanning tunneling microcopy (STM)
460 525 528 531 534
Binding Energy (eV) (−0.377 eV) and a smaller O–C–O bond angle (126.0°) for
the adsorption of CO2 than the stoichiometric Sr2Bi2Nb2-化学计量，化学计
TiO12 (−0.125 eV and 179.0°). Huygh et al. [274] in-算
vestigated the adsorption, dissociation, and diffusion of
CO2 on the (001) surface of anatase (TiO2) with DFT
侻钛矿
calculations (Fig. 15). A new highly stable adsorption
configuration of CO2, residing one of the O atoms of CO2
inside the OVs, was proposed with the introduction of
OVs, leading to a stronger activation of C–O bond and a
possible exothermic dissociation of CO2. Such a config-
uration decreases the barrier of the CO2 dissociation re-
−1
action from >45 to 22.2 kcal mol . Werner et al. [117]
examined how OVs within CeO2 facilitated the selective
hydrogenation that converted alkynes to alkenes. The
interaction between H2 and CeO2, a crucial aspect of the
hydrogenation reaction, depends strongly on OVs. Ac-
cording to nuclear reaction analysis (NRA) and DFT
calculations, hydrogen species remain as hydroxyls on the
surface of stoichiometric CeO2 but get incorporated into
the interior of OVs-rich CeO2−x in the form of hydride
氢化物
species. In fact, enhanced adsorption and molecular ac-
tivation commonly occur simultaneously in N2 fixation,
CO2 reduction, and H2O splitting in the presence of OVs.
The industrial Haber–Bosch process for N2 fixation to
produce NH3 requires hash conditions (15–25 MPa,
300–550°C), and N2 fixation under mild conditions re-
mains to be conquered in industry [265]. Prior studies
have demonstrated efficient electron transfer from OVs

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350 *C 70 %
m ;m m< m m ®
#
® m <& ®> m ®
©
m
m> ® mm®
<#>
250 “C 35 %
.<
MnO 110)

450 °C 16 %

-
r
2.6 2.8 3.0 3.2 3.4
Oxygen vacancies (relative ratio)
b
I MnO2(110)-12Oys

MnO? ( 110 ) with BOVS

Recombination of
electron and hole
P m MnO2(110)-16OVs

9"i9 WiW
Photocurr«nt
OUTER CIRCUIT

Figure 14 (a) Energy diagram of In2O3−n with different amounts of OVs; (b) schematic illustration of how excess OVs affect the transfer of
photoelectron in photon-to-electron conversion processes; (c) plot of the best IPCE efficiency with visible light (>400 nm) of In2O3 obtained by
calcination in air at 250, 350, 450°C, as a function of the relative OV amount. Adapted with permission from Ref. [251], Copyright 2013, American
Association for the Advancement of Science (AAAS); (d) the charge density of MnO2(110) varying with the number of OVs; (e) structural model and
total charge density of β-MnO2 (110) with 0, 4, 8, 12, and 16 OVs, respectively. Adapted with permission from Ref. [252], Copyright 2015, American
Chemical Society.

a
4 «; [001]
[ 010]

OV1 OV4
b

[100 ]

OV 2
OV3 /

f#

&s fes 3? $>5 fe

D- OVl( l) D- OVl(ll ) D- OVl(lll)
* D- OV 2(l) D-OV3 ( l )
*
D- OV3 (ll)

Figure 15 Different adsorption configurations of CO2 on the anatase (001) surface (a) without and (c) with different OVs, in side view and top view
(upper and lower panels, respectively). Ti = blue, OTiO2 = red, OCO2 = red with yellow plus sign, C = brown. B(I) is a strong chemisorbed monodentate
carbonate configuration, and L(I), L(II), and L(III) are physisorbed configurations; (b) different OVs on an anatase (001) TiO2 surface (Ti = gray, O =
red, OV = yellow.). Adapted with permission from Ref. [274], Copyright 2016, American Chemical Society.

to N2, which may promote N2 adsorption and activate the the chemical adsorption of N2 on defective Mo sites via
N≡N triple bond [265,275,276]. Zhang et al. [212] also electron donation. Energy change calculations reveal that
showed how the OVs in atomic layered MoO2 expedited in the presence of OVs on MoO2, N2 has a low adsorption

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 15
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

energy of −1.05 eV and is much more easily adsorbed. In

contrast, the adsorption energy for N2 on OV-free MoO2
reaches as high as 1.50 eV. Hence, the OVs-MoO2 catalyst
exhibits high activity and selectivity in N2 fixation. Li et
al. [265] further demonstrated the efficient fixation of N2
to give NH3 using visible light illumination and BiOBr
nanosheets with OVs. Notably, the reaction proceeds
without any organic scavenger or precious metal cocata-
lyst, because the OVs activate the adsorption of N2 and
increase its bond length to 1.133 Å with the interfacial
electrons transferred from the excited BiOBr nanosheets.
Han et al. [277] accomplished the electrochemical
synthesis of NH3 over TiO2 with abundant OVs. The OVs
simultaneously enhance N2 adsorption and activate the
N≡N triple bond, thus promoting the nitrogen reduction
reaction (NRR) (Fig. 16). They used DFT studies to reveal
that the surface OVs stabilized *NNH, a highly unstable
and potentially rate-determining intermediate, hence
dramatically lowering the ΔGPDS of the NRR by
1.4–1.7 eV. Without doubt, novel catalysts that exploit the
benefits of OVs create unprecedented opportunities to fix
atmospheric N2 through less energy-demanding photo-
or electro-chemical processes.
Converting CO2 to value-added chemicals offers a
sustainable solution for carbon cycling and is of sig-
nificance in solving environmental problems and energy
crisis [278,279]. Yang et al. [267] found in their sys-
tematic theoretical calculations of the absorption and
activation of CO2 on OVs-rich Bi2MoO6 (Fig. 17) that the
OVs can decrease the adsorption energy of CO2 and that
the localized electrons around the OVs tended to be in-
jected into CO2 after the adsorption of CO2, thus facil-
itating the further hydrogenation of the intermediate *CO
to form CH4. Geng et al. [227] developed an efficient
strategy to facilitate CO2 reduction by introducing OVs
into electrocatalysts, and mechanistically demonstrated
that the OVs improved CO production by increasing the
anatase anatase OV -
( 0.42) ( 0.09)
I
rutile -
rutile OV
( 0.41) ( 0.34)
Figure 16 The optimized geometries (side view) and free energy
changes (in eV) of *N2 on pristine and OV-containing TiO2. Cyan, red,
and blue spheres indicate Ti, O, and N atoms, respectively. Adapted with
permission from Ref. [277], Copyright 2019, Elsevier.
binding strength of CO2 and reducing the barrier of CO2
activation.
The photocatalytic splitting of water to generate hy-
drogen helps combat the energy crisis and environmental
problems caused by the overuse of fossil fuels and is a
desirable means to access renewable energy. Li et al. [280]
demonstrated that the adsorption and activation degree
of H2O were different on different surfaces of BiOCl with
OVs: H2O was dissociatively adsorbed on the OVs of the
(010) surface but molecularly absorbed on the OVs of the
(001) surface (Fig. 18). In situ water contact angle mea- 水接触角
surement clearly shows different states of H2O molecules
on the (010) and (001) surfaces, and verifies that the (001)
surface is more hydrophilic. According to DFT results,
亲水性
OVs help cleave the O–H bond on the BiOCl (010) sur-

a4 c
3 •feS&fia&r
>o 2 0.15 e 0.07 e
0 2p-
Mo - 4 d
Slab co2 Slab
0) 1 BI4p

<1) ) •

c
LU 0 ; r
1.26 A 1.26A 1
Pv
1- 30 A

15 30 45 60
Bi ° ° °
/ \/ \/ \
Bi Bi Bi
..
DOS ( a u )

Figure 17 (a) Calculated band structures and DOS of Bi2MoO6-OVs, and adsorption of CO2 on (b) OVs-rich and (c) OV-free Bi2MoO6. The yellow
and blue iso-surfaces represent the charge accumulation and depletion in the space. Adapted with permission from Ref. [267], Copyright 2019,
Elsevier.

16 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
 SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

c
Hb
0^
w
\ \ 1.89 A
/ H3 i cP
Bi3c s.
Oac
No
AE = -0.45 eV, Ap = -0.31 e
4>
* OwHa = 0.99 A, OwHb = 0.98 A

Hb d °- ——
15 TDOS
PDOS on H.2OOIMOc
/ if ) 1
— 0‘
PDOS on H.O
2 010OV

O °
Bi
2c

Bi? r \ Q
50 -
Bisc Vfl edge CB edge

o i
AE = -1.24 eV, Ap = 0.89 e
-5 -4 -3 -2 -1 0 1 2 3 4 5
OwHa = 0.98 A, OwHb = 2.60 A Energy (eV )

3.02 A
/
H

/ ,a
-'
2.05 A !
ow
w
9
Q &
O

O
:

o 0'H
Bi« VBi/ 4c
B 4C
' Pa
AE = -0.11 eV, Ap = 0.08 e Chaf ition
from OV to H20
OwHa = 0.97 A, OwHb = 0.97 A j

Ob ^ 150 - — TDOS
— PDOS on HO
2 ~001 MB

/ Hb — PDOS on H O2 -
001 OV
CO 1 0‘
Ob /
o °
, AH
75
^

'
°^\ Q
50 -
Bi3c VB edge CB edge

o 4 \
AE = -0.53 eV, Ap = 0.42 e
-5 -4 -3 -2 -1 0 1 2 3 4 5
OwHa = 1.00 A, OwHb = 1.01 A Energy (eV )

Figure 18 Theoretical study of water adsorption on the defect-free BiOCl (a) (100) and (e) (010) surfaces; theoretical study of water adsorption on the
BiOCl (b) (100) and (f) (010) surfaces with an OV; the corresponding charge density difference is given in (c) and (g) for the BiOCl (100) and (010)
surfaces respectively; PDOS of H2O on the (d) (100) and (h) (010) surface of BiOCl with different adsorption structures (HBs: hydrogen bond; ΔE: the
water adsorption energy; Δρ: the Bader charge change of the adsorbed water). Adapted with permission from Ref. [280], Copyright 2016, American
Chemical Society.

face but hinders the cleavage on the (001) surface.
Catalytic oxygen reduction reaction (ORR) is crucial to
many energy conversion processes ranging from the
sustainable production of hydrogen peroxide (H2O2) to
fuel cell applications [281]. In case of LaMnO3 and
LaxSr1−xMnO3, Staykov et al. [281] reported that OVs
allowed easier charge transfer from the catalyst surface to
the adsorbates and thus accelerated the O2 reduction ki-
动力学 netics. However, thorough theoretical understanding is
still lacking regarding the impact of OVs on the genera-
tion of active oxygen and the catalytic cycle of ORR,
which limits the rational design of point defect catalysts.
Yang et al. [116] revealed that OVs promoted O2 acti-
vation on the surface of perovskite oxide for low-tem- 钙钛矿
perature CO oxidation. Specifically, they found that O2
was more favorably adsorbed and activated on surfaces
−
with OVs via a one-electron transfer process to form O ,
−
thus increasing the richness of active O to promote the
low-temperature oxidation of CO.
Catalysis kinetics
Catalytic reactions that may generate various products at
the same time require further separation and purification,
thus creating extra trouble to industrial application.

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 17
 REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

a 0.9
Needless to say, developing catalysts with excellent se-
lectivity to give the desired product specifically is crucial 0.6

for synthetic applications, but this remains a challenge. 0.3

/ *N \
Prior studies have demonstrated in a number of cases > /*HNNHV
3L 0.0
h i *
how OVs advance the selectivity of catalytic reactions > / *NH :
U) .
d -
[117,282–285]. For instance, whereas commercial noble ± 0.3
* HNNH2
c>
metal-based catalysts suffer from poor ability to trans- m 0.6
d> - ,1 *NNH
*NNH2 \ .
SV
oiHra" *NH*2
|

form NOx to N2 [212,286], OVs-rich Pt/CeO2 and Rh/ 2?

Li- -0.9 £ [
Distal Path
JL
CeO2 afford high selectivity in the catalytic conversion of Alternating Path
*H2NNH2
NO to N2 [287]. -1.2 *N2
Distal/ Alternating Path

Generally, for a catalytic reaction that may lead to -1.5

b 3 *NNH
multiple products, the reaction pathway with smallest
energy barrier is taken among multiple alternatives. It is 2
thus not surprising to see that OVs promote the catalytic >Q
selectivity, since they always affect the potential energy U)
barriers of catalytic reactions. For instance, Zhang et al. <1)
c 0
[212] disclosed that OVs-MoO2 had a high selectivity LU *
O
toward the reduction of N2 (NRR), as OVs can, via the
o -1
远郊 Li.

混合
distal/alternating hybrid path, selectively stabilize N2H* to
form NNH2* and then facilitate a direct protonation of
NNH2* to HN2H2* (Fig. 19). The activation energy of the
rate-limiting step is thus reduced to 0.36 from 1.49 eV as
is in the case of perfect MoO2.
Activating CO2 by OVs impressively shows how OVs
affect the selectivity in a complicated catalytic reaction.
Two possible pathways have been proposed for CO2 re-
duction over TiO2 surface, i.e., the fast-hydrogenation
(FH) pathway and the fast-deoxygenation (FdO) path-
-2
质子化 -3 OVs Free M 0O2 OVs-Rich M0O2
Figure 19 (a) The free energy diagram for different NRR pathways on
OVs-rich MoO2. In the distal pathway (blue dash line), the protonation
of NNH* to HNNH* has an energy barrier of ΔG = 0.69 eV, and de-
protonation of N2H2* to form N* species has ΔG = 0.54 eV. However,
the energy barrier is effectively decreased in the distal/alternative hybrid
path to ΔG = 0.36 eV; (b) energy profiles for electrocatalytic N2 reduc-
tion on the surfaces of MoO2 with no OV, rich OVs, and excessive OVs.
Adapted with permission from Ref. [212], Copyright 2019, Elsevier.

way. In a mechanistic study, Ji et al. [261] carried out

first-principles calculations to examine the pathways of
CO2 reduction on perfect and defective anatase TiO2
(101) surfaces. Because of unfavorable energy barrier, the
FdO pathway can proceed on neither the perfect surface
nor the defective surface. In contrast, the defective surface
has a much lower barrier for the deoxygenation process
in the FH pathway. In the presence of OVs, the catalytic
reaction needs fewer protons to promote the formation of
CH4 from CO, because the O in CO does not need two
extra protons to form H2O but will simply stay in the
OVs. Yang et al. [267] demonstrated with DFT and CO2-
TPD spectra that the hydrogenation of *CHO to CH4 was
more thermodynamically favorable on OVs-rich Bi2MoO6
than on perfect Bi2MoO6. With the charge density dif-
ference introduced by OVs, electrons will be injected into
adsorbed CO2, increasing the C–O bond length from 1.18
to 1.26 or 1.29 Å. In the electrocatalytic reduction of CO2
to formate [288], OVs-rich Co3O4 has a lower onset po-
甲酸
tential of about 0.78 V and a Tafel slope of 37 mV dec ,
whereas perfect Co3O4 has an onset potential of 0.81 V
−1
and a Tafel slope of 48 mV dec . According to DFT
calculations, OVs reduce the energy barrier of the rate-
limiting step from 0.51 to 0.40 eV by stabilizing the
−
HCOO * intermediate (Fig. 20).
The synthesis of value-added products having two or
more carbons (e.g., gasoline) directly from CO2 is far
more challenging than the hydrogenation of CO2 to give
C1 chemicals, because of the inertness of CO2 as well as 惰性
the high C–C coupling barrier. Gao et al. [289] developed
a bifunctional catalyst consisting of reducible indium
oxide (In2O3) and zeolites that has high selectivity for 沸石
gasoline-range hydrocarbons (78.6%) with very low me-
甲烷
thane selectivity (1%). The OVs on In2O3 surfaces activate
both CO2 and H2 to form methanol, and C–C coupling
甲醇
occurs subsequently inside the zeolite pores to produce
gasoline-range hydrocarbons with a high octane number.
辛烷
Multicomponent catalytic platforms
−1
The integration of multiple functional units of catalysis
into complex architecture has sparked rising interest for
engineering sophisticated nanomaterials [290–292]. In-

18 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

o
Pt e-
OV
e CB
0

Vacancy
O2+H*
Figure 20 Calculated free energy (in eV) diagrams for the electro-
chemical reduction of CO2 to formate on (a) Co3O4 with OVs and (b)
intact Co3O4 single unit cell layers. The first step is an electron transfer
•− Figure 21 Mechanisms for the photoreduction of CO2 with H2O vapor
to form CO2 and the second step involves a simultaneous proton/
electron transfer, the product of which gives formic acid. Asterisk de- over highly dispersed Pt nanoparticles on ultrathin TiO2 support
notes the active site. The spheres in white, red, grey, and light blue Adapted with permission from ref. [295], Copyright 2018, Elsevier.
represent H, O, C, and Co atoms, respectively. Adapted with permission
from Ref. [288], Copyright 2017, Nature Publishing Group.

results in a faster separation of photogenerated electrons-

deed, OVs also engage in multicomponent catalytic
platforms to endow reactions with new catalytic me-
chanisms [293,294].
Recently, atomically dispersed catalysts have attracted
tremendous attention for their unique structures and
maximized atom utilization. Utilizing noble metals in
ultra-small forms (ultrafine nanoparticles, clusters, single 团簇 the adsorption of activated bent CO2 as well as CO2
atoms) is an effective strategy to increase their usage ef-
ficiency and catalytic activity. Liu et al. [295] demon-
strated that OVs-rich ultrathin TiO2 decorated with
highly dispersed Pt nanoparticles exhibited excellent
photocatalytic activity for the conversion of CO2 to CH4
−1 −1
and CO with a total electronic yield of 666.6 μmol g h .
Electron transfer from the OVs-rich ultrathin TiO2 to Pt
holes, and the OVs also enable stronger adsorption of
CO2 (Fig. 21).
Chen et al. [296] found that in the CO2 reduction over
single Cu atom on OVs-rich TiO2, the dissociation of CO2
preferentially occured at the Cu/OV/TiO2 interface. The
combination of Cu atoms with OVs-rich TiO2 facilitates
dissociation. Specifically, the adsorption intensity of bent
CO2 ranks in the order of Cu/OV/TiO2 > OV/TiO2 > Cu/
TiO2 > TiO2 (Fig. 22). The as-formed Cu/OV complex
can lower the reaction barrier for CO2 dissociation (CO2*
→ CO* + O*) to a very low level (0.10–0.19 eV) to ex-
pedite the production of CO.
The study on Cu/CeO2−x also highlights how multi-

S1 - Ti02 S 2 - Cu/Ti02 R1 - Ov R 2 - Cu in Ov R3 - Cu near Ov R4 - Cu far Ov

-0.20 eV - 0.28 eV -1.28 eV -0.85 eV -1.30 eV -1.29 eV

Figure 22 Most stable adsorption geometries and adsorption energies of bent CO2 on (S1) a stoichiometric TiO2 surface, (S2) a stoichiometric TiO2
surface with a Cu atom, (R1) a reduced TiO2 surface with OV, (R2) a reduced TiO2 surface with a Cu atom in an OV, (R3) a reduced TiO2 surface with
Cu near an OV, and (R4) a reduced TiO2 surface with Cu far from OV. Adapted with permission from Ref. [296], Copyright 2018, American
Chemical Society.

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 19
 REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials

component catalytic platforms can aid the discovery of Manipulating OVs, the prerequisite to elucidating me-
new mechanisms to promote CO2 reduction. Varandili et chanistic features in catalytic activity, remains a daunting
al. [259] demonstrated how the unique active sites at the challenge. To date, it remains difficult to attain fine
Cu/CeO2−x interface stabilized CO2 intermediates with a control over the concentration and spatial location of 空间
bidentate adsorption involving both CeO2−x OV sites and OVs in a given catalyst while maintaining the structural
Cu, which promoted the activity of CO2, improved the integrity of the catalyst precursor. First of all, it must be
selectivity for generating methane, and allowed reaction noted that the contribution of OVs depends highly on
engineering beyond the limits of scaling relationship their concentration. Excessive OVs trap electrons and
(Fig. 23). restrain electronic mobility, which explains why catalysts
协同
Synergy may also occur between two different types of with an unduly high amount of OVs have poorer pho-
defects. Some cationic defects also exist in some oxygen- tocatalytic performance than those with a moderate
deficient materials. Wu et al. [297] built a new homo- amount of OVs [251]. Excessive OVs may introduce a
junction of TiO2 and proved both experimentally and new impurity band with unlocalized MO that can capture
同质结
with DFT that the oxygen and titanium vacancies chan- electrons excited from the VB and prevent them from
ged the charge density of the resulting TiO2, and de- arriving in the CB, thus decreasing the electronic con-
monstrated the performance of the homojunction in ductivity [51,252]. Lately, researchers start to realize that
photocurrent generation, photocatalysis, and energy sto- OVs may differ in their locations (on the surface or in the
rage (Fig. 24). bulk lattice). It is generally believed that the surface OVs
contribute to catalytic activity whereas the bulk OVs act
CHALLENGES AND PERSPECTIVES as a charge capture center to impede electron transfer
Engineering OVs-mediated catalysis requires a thorough [232]. Lv et al. [107] found that the surface OVs greatly
understanding of OVs regarding both their formation improve the photocatalytic performance of BiPO4−x and
and their modes of action. Atomic level details on the enhance its response to visible light by broadening the VB
interactions between metal oxides and defects need fur- and narrowing the band gap, whereas the bulk OVs act as
ther elucidation, because understanding these various the charge capture center and inhibit electron-hole se-
阐明
features will shed light on rational catalyst design. How- paration. Nonetheless, the bulk OVs are also considered
ever, to date, many aspects of OVs still remain significant to play a positive role in boosting visible light harvesting,
scientific challenges and call for exploration. narrowing Eg, and slightly restraining the recombination

05
c > A9
CD
t>* o. - •
—
Cu CeO / ?i
HDs
Scaling relation
Cu,
. Au
CD
S
| - - 5-
°
O)
c
TJ -1.0-

_
Pj
£ PI
CD Ni
o -15- Rh
i
O
b 0 CH 0H (aq) - 2.0-
}
-20 -1.5 -1 0 -0 5 0

/ CO * Binding Energy / eV
-2 - OCO* CO*
+
OH *
CHO * d 1.0'
+
-4 - >
>CD
OH * CHO * <D
> . 05- •Scaling relation
—
Cu/CeO.,, HDs
SnO,

-6 - H,CO * s> "

ReOj ifOj
0 <D T Oj
<t CH3OH ( aq) c
LU
0
MoO
' RuO?
-8 - H 3CO * CO
c -0.5-
T3 wo . ,

C
-10 - ovRHE m -1.0-
- 1.2 VRHE CH,(aq)
o* O NbO,
0H’ H 0_ o 15 -
-12 - " T "OJ
; M

"
X

0 2 4 6 8
-2.0- - 2.0 -1.5 -10 -0.5 0
(e ) transferred OH* Binding Energy / eV

Figure 23 (a) CO2 reduction on Cu/CeO2−x heterodimers (HDs) for methane evolution at the active sites on the interface; (b) thermodynamics of
methane and methanol evolution at 0 and −1.2VRHE; (c, d) scaling relationship of CO*/CHO* and H2CO*/OH* is broken due to a unique bidentate
adsorption. Adapted with permission from Ref. [259], Copyright 2019, American Chemical Society.

20 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
SCIENCE CHINA Materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . REVIEWS

a > k Ti 2p3/2 b
cT 6
0 « •• Ti02-A E On
P5
3 {T Off
I • *
-0.1 '
>
3 .0.2
LU -
34 -
*
55 3
‘
c
LI
< * •*
TiOr350
&
»
<D
• 0.3 * 2 -
c
-0.4 « TiO2-550 a> 1
-
••••
ll a
•
TiOr750 oO
-0.5 ' 0

c y/ - d
Q 1s
Tj 2p3/2
v

—
jjj TiO2-350

-
> -
TiO2 550
K
,7
1

457 458 459 460 528 529 530 531 532

Binding Energy(eV)
2.80e 1 f

•
Ct •
Cl
1.85e 1

9.00e-2

S.OOe-3

m. U -1.00e 1
Figure 24 (a) The chemical shift of Ti 2p3/2 for TiO2-A, TiO2-350, TiO2-550, and TiO2-750; (b) the transient photocurrent responses of TiO2-A, TiO2-
350, TiO2-550, and TiO2-750 vs. SCE under UV-vis irradiation; (c) Ti 2p3/2 and O 1s XPS spectra of TiO2-350 and TiO2-550; (d) simulated geometric
structures of TiO2 with junction of O vacancies and Ti vacancies; (e) charge density difference between normal TiO2 and TiO2 with junction of OVs
and Ti vacancies. Adapted with permission from Ref. [297], Copyright 2018, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

of electrons and holes [298,299].
Because OVs in designed systems often exhibit multiple
optical, electrical, and catalytic functions, the specific
impact of OVs on catalysis is at times elusive and con-
troversial. As such, conflicting findings are not un-
common regarding the connection between OVs and
catalyst properties.
Identification of the real active sites of OVs-rich cata-
lyst is also crucial for effective catalyst design. For in-
stance, numerous studies suggested that OVs can be
created by ion doping and the newly-formed OVs con-
tributed to catalytic activity, but it remained controversial
in some cases whether the OVs or the dopant ions were
the active sites. More control experiments and systematic
investigations are needed to identify the contribution of
dopant to thus clearly establish the roles of OVs in the
catalytic reaction. It is also worth mentioning that a sy-
nergy may exist between OVs and dopant ions to improve
the catalytic activity [300,301].
Stability is a significant feature of advanced catalysts,
but OVs are subject to oxidation during catalytic reac-
tions, which can reduce catalytic activity. Surface OVs can
be refilled when the oxides seize O atoms from water or
molecular oxygen to render the original OV-free com-
position [302]. A number of strategies have been pro-
posed to address the susceptibility of OVs to oxidation

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020 21
REVIEWS . . . . . . . . . . . . . . . . . . . . . . . . . . SCIENCE CHINA Materials
[303,304]. For instance, Wang et al. [304] found that
carbon coating can stabilize the surface OVs of TiO2
nanorods [303]. Ion doping has also been adopted to
stabilize OVs. However, a general approach to stabilize
OVs in catalytic reactions is still lacking. A fundamental
understanding of how the structural factors of the catalyst
(e.g., size, lattice strain, dimension, surface structure, etc.)
impact the stability of OVs is essential.
To summarize, challenges and opportunities abound in
the exploration of advanced OVs-mediated photo-
catalysts. As the old saying goes, where there is a will,
there is a way. Progress in this field can considerably
improve the understanding of point defects and the de-
sign of related materials, and eventually help secure clean
energy and lead to breakthroughs in environmental ap-
plications.
Received 20 January 2020; accepted 17 March 2020;
published online 19 May 2020
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Acknowledgements This work was financially supported by the Na-
tional Natural Science Foundation of China (U1905215, 51772053 and
51672046).
Author contributions Zhuang Z and Yu Y conceptualized the work,
and wrote and revised the manuscript. Zhuang G and Chen Y collected
and summarized the literatures, and contributed to the manuscript
writing. Yu J revised the manuscript and offered creative proposal for
improving the depth and coverage of the review. All authors contributed
to the general discussion.
Conflict of interest The authors declare no conflict of interest.
Guoxin Zhuang received his BSc in materials
science and engineering from Fuzhou University.
He is currently pursuing his PhD degree at
Fuzhou University under the supervision of Prof.
Yu and Prof. Zhuang. His research focuses on the
design of MOFs and catalysts for CO2 photo-
reduction.
30 © Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2020
Zanyong Zhuang received his BSc in chemistry
from Xiamen University, and his PhD in 2011
from Fujian Institute of Research on the Struc-
ture of Matter (FJIRSM), Chinese Academy of
Sciences (CAS). He became an associate re-
searcher in FJIRSM, CAS in 2014. Currently he is
an associate professor at Fuzhou University. His
research interests include the design of low-
dimensional nanostructures, nanocrystals growth
and assembly, comprehensive utilization of solid
waste, and the related catalytic topics.
Yan Yu received her BSc, MSc and PhD degrees
from Fuzhou University. She was a postdoctoral
fellow in FJIRSM, CAS, and became a Professor
at Fuzhou University in 2011. Her research in-
terests include semiconductors, photocatalysis,
environmental purification materials, compre-
hensive utilization of solid waste, and the related
topics.
Jiaguo Yu received his BSc and MSc degrees in
chemistry from the Central China Normal Uni-
versity and Xi’an Jiaotong University, respec-
tively, and his PhD in materials science in 2000
from Wuhan University of Technology. In 2000,
he became a Professor at Wuhan University of
Technology. He was a postdoctoral fellow at the
Chinese University of Hong Kong from 2001 to
2004, a visiting scientist from 2005 to 2006 at the
University of Bristol, and a visiting scholar from
2007 to 2008 at the University of Texas, Austin.
His research interests include semiconductors, photocatalysis, photo-
catalytic hydrogen production, solar fuels, dye-sensitized solar cells,
adsorption, CO2 capture, graphene, and the related topics.
金属氧化物中的氧空位: 先进催化剂设计的新进
展
1,2 1,2 1,2* 1,2* 3*
庄国鑫 , 陈雅文 , 庄赞勇 , 于岩 , 余家国
摘要 高效、稳定的催化材料有望解决日益严峻的环境污染和能
源危机问题. 金属氧化物具有高稳定性、低成本以及高催化活性
等优点, 在能源转换和环境净化等领域有广阔的应用前景, 已广泛
应用于H 2 O裂解、CO 2 还原、固氮以及污染物的高级氧化等催化
领域中. 氧空位作为金属氧化物中普遍存在的一种内在缺陷, 被证
实可显著影响甚至改变材料的物理化学性质, 是调控催化剂结构
和催化性能的有效手段. 深入了解催化材料氧空位的调节以及氧
空位对催化性能的作用机制, 为设计出高效金属氧化物催化剂提
供重要理论基础. 本文综述了近年来调控氧空位的基本原理和控
制因素, 介绍了氧空位的结构与催化活性的基本关系, 包括如何影
响材料的光吸收、电荷分离和反应物的吸附活化等, 着重介绍了
氧空位的形成机制及其对金属氧化物催化特性的影响. 同时, 我们
还对多组分催化过程中, 氧空位与其他类型催化组分间的协同催
化机制进行了总结. 最后, 本文提出了材料缺陷工程在催化领域面
临的机遇和挑战.